Gel composition

ABSTRACT

(2,4,6-TRI(O=)HEXAHYDRO-S-TRIAZIN-1,3,5-TRIYL)M (2,4,6-   TRI(O=),1-X-HEXAHYDRO-S-TRIAZIN-3,5-DIYL)N   -(R)(2M+N+1)- -(A)(M+2)   A GEL COMPOSITION SUFFICIENTLY STABLE TO SUPPORT ITS OWN WEIGHT HAVING ELASTICITY AND COHESIVE CHARACTER PRODUCED BY REACTING AT A PH ABOVE 7, AN ALKALI METAL HYDRODIDE OR ALKALINE EARTH METAL HYDROXIDE WITH A COMPOUND WHICH CONTAINS POLYISOCYANURATE SALT GROUPS, TRISUBSTITUTED ISOCYANURATE RINGS AND END GROUPS SELECTED FROM: ISOCYANATE, URETHANE, UREA AND AMINO GROUPS, IN THE PRESENCE OF HYDROXYETHYL CELLULOSE.

Jan.. 29,

c. T. PRESLEY ETAL yym@ GFL COMPOSITION Filed Aug. 23, 1971 2 Sheets-Sheet 1 (S= SATURATED l ALKYL: CH3 s 9 @v PoLYMEmc= v (WHERE n MAY as: FROM 1 o so) INVENTORS PERRY A. ARGABRIGHT C. TRAVIS LEY jm- 29 W74 c. T, PRESLEY ETAL $78993@ GFL COMPOSITION Filed Aug. 25, 1971 2 Sheets-Sheet 2 /CH-s C3H7 CHB- crwcH-CH CH2-GEC@ c:20mn Hl INVENTORS "s CH3 PERRY A. ARGABRIGHT cH l a@ 9 L L w fr 3,789,010 GEL COMPOSITION C. Travis Presley, Littleton, Perry Argabright, Larkspur, and Ronald E. Smith, Littleton, Colo., assgnors to Marathon Oil Company, Findlay, Ohio Filed Aug. 23, 1971, Ser. No. 173,759 Int. Cl. B01j 13/00 U.S. Cl. 252-316 6 Claims ABSTRACT OF THE DISCLOSURE A gel composition suiciently stable to support its own weight having elasticity and cohesive character produced by reacting at a pH above 7, an :alkali metal hydroxide or alkaline earth metal hydroxide with a compound which contains polyisocyanurate salt groups, trisubstituted isocyanurate rings and end groups selected from: isocyanate, urethane, urea and amino groups, in the presence of hydroxyethyl cellulose.

CROSS REFERENCES TO RELATED APPLICATIONS The following U.S. Patent application relates to compounds and uses which are generally related to the present invention: Ser. No. 173,892, filed Aug. 23, 1971.

BACKGROUND OF THE INVENTION Field of the invention The present invention relates generally to the ield of isocyanurate-containing organic compositions generally classified with Class 260, subclasses -248 and 88.3 of the United States Patent Oliice, and to organic gels generally classified in Class 252-316.

Description of the prior art The present invention relates to a new class of compositions which are useful as gels, e.g., in forming plugs such as for pipe line separation pigs etc. These compositions are produced by contacting hydroxyethyl cellulose with a compound characterized by containing in a single molecule the following groups:

metal isocyanurate,

N O rsf O N N...

with or without isocyanurate,

(ufff) The gelling agents of the present invention have the advantage of giving a controllable time to onset of gelation. That is, by merely adjusting the pH of the initial United .States Patent O 3,789,010 Patented Jan. 29, 1974 ICC solution, the gelation time may be controlled, a feature not available with conventional systems.

The isocyanurate compounds of the present invention have the general structure shown in FIG. 1;

whe re R=divalent hydrocarbon or substituted hydrocarbon radical as described below and exemplified in FIG. 2.

X=a metal, or hydrogen or quaternary ammonium (which, for the purposes of this invention, acts like a metal) or a combination thereof. Particularly preferred are hydrogen, quaternary ammonium and metals selected from the following groups of the Periodic Table; Ia, Ib, IIa, IIb, IIla, IlIb, IVa, IVb, Va, Vb, Vla; including such metals as Li, Na, K, Rb, Cs, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Sc, Y, La, and the other rare earths, Ac, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, M0, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, and Ir.

A=a monovalent organic radical selected from the following: isocyanate (-NCO), urethane (-NHCOZRL urea (-NHCONHR), amino (-NHZ), -NHR', -NR2, or R', for example.

R|=monovalent hydrocarbon or substituted hydrocarbon radical, as discussed below;

m=average number of trisubstituted isocyanurate rings and is a positive number from 0 to about 400, and most preferably from 0 to about 200.

n=average number of isocyanuric acid and/or isocyanurate salt groups and is a positive number from above l to about 10,000, more preferably from 2 to about 1000, and most preferably from 3 to about 100.

2m+n+l=average number of divalent R groups and is a positive integer from 2 to about 11,000, more preferably from 3 to about 1,100 and most preferably from 4 to about 140.

ml+2=average number of A groups and is a positive integer from 2 to about 2,000, more preferably from 2 to about 400 and most preferably from 2 to about 200;

etc

R and/or R can be substituted with groups that do not interfere in the products subsequent utility or in its preparation. Examples of such noninterfering groups are: -NO2, Cl, F, Br, I, CN, -CO2R", CO-R, -O-R" `SR, -N-RZ, -CONR2", -SO'3R,

etc. where yR may be hydrogen, lower alkyl (e.g., ethyl, hexyl) or aryl (e.g. monovalent radicals corresponding to the aryl radicals described in FIG. 2. The examples of R (shown in FIG. 2) are set forth for purposes of elucidation, not restriction. Y

It will be recognized that the values of m and n `described above are on the basis of the integers which will be used to describe a single molecule. In actual practice, the invention will involve mixtures of molecules of the general form described above. Thus, the average value of m lfor the mixture may be from about 1 to about 2000, more preferably from about l to 400, and most preferably from about 1 to 200; the average value of n may be from about 0.5 to 10,000, more preferably from about 0.5 to 1000, and most preferably from about 0.5 to 100.

Utility of the invention The present invention relates to a new and novel class of gels, their preparation, and processes for their use. For example, the compositions of the present invention can be used as gels in pipe line separation devices, e.g., according to the techniques of U.S. Pats. 3,473,572; 3,225,787 and 3,209,771, and in electrophoresis gels such as those taught in U.S. Pat. 3,576,727. Other uses include: cast iilms, encapsulating media, e.g., for electronic devices, molds, fillers for water beds and other filled plastic iiexible envelopes, etc.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. l shows the general formula of the organic starting materials of the present invention.

FIGS. 2 and 3 exemplify some of the possible structures of R groups of the starting materials and products of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS It has been discovered that aqueous solutions of the aforementioned polyisocyanurate salts, of the general formula shown in FIG. yl, (where the lettered groups are as described above under Summary of the Invention), when contacted with hydroxyethyl cellulose under basic conditions, (i.e., pH in excess of 7) give the gels of the present invention.

Starting materials The starting materials for the present invention are:

Salts of polyisocyanuric acids-These areA produced according to the techniques taught in copending U.S. Pat. 3,573,259, by reacting a metal cyanate and an organic diisocyanate'in the' presence of an aprotic vsolvent to form isocyanurate-contaimng polyisocyanate metal salts. Preferably 0.3 to about 50% byweight, more preferably 0.5 to about 25% by weight, and most preferably 1.0 to about 10% by weight of polyisocyanurate salts will be used in the aqueous solution.

Hydroxyethyl cellulose-The hydroxyethyl cellulose used in the present invention can be of commercial quality such as that marketed by Hercules Powder Company of Wilmington, Delaware, and described in its brochure 855 6M 7-63 Natrosol Hydroxyethylcellulose. In general, about 0.15 to about 20, more preferably 0.20 to about l5, and most preferably 0.25 to about 3% by weight of hydroxyethyl cellulose will be mixed with the aforementioned isocyanurate salt starting materials. In general, high molecular weight HEC will require less HEC for gelation.

Bases-While not narrowly critical, the bases employed with the present invention will preferably be alkali metals, metal hydroxides, e.g., NaOH, KOH, LiOH, and alkaline earth metal hydroxides, e.g., Ca(OH)2, etc. The alkali metal hydroxides will be Vmore preferred, with sodium hydroxide being the most preferred of the bases. In general, the pH. will be adjusted im@ a vrange above 7,

more preferably from about 7.5 to about 15, and most preferably from about 12 Vto about l5.

Reaction Media- Water or mixtures of water and an alcohol, ketone, ester, amide, sulfoxide, sulfone, etc.

Temperature.-While not narrowly critical, temperatures in the range from 0 to about 65 C. are preferred, with l0 to 50 C. being more preferred and l540 C. being most preferred. The lower limit is generally the freezing point'of the solution and the upper limit is generally the thermal instability point of the gel at the re-A EXAMPLE I Preparation of polyisocyanurate salt To a stirred slurry of 82.4 KOCN (1.02 mole) in 2000 Inl. of dimethylformamide (DMF) at 75 C., 161 g. of tolylene diisocyanate (0.93 mole) is added at a rate of 0.42 ml./min. by means of a syringe pump.

Aryl/end group 1 ratio Average Percent (2m-l-n-l-1 Mol. Wt. Product yield 1' m+2 (minimum) 'DMF insolublel 93.3 17.0 8 00 DMF soluble 6. 3 1. 9 95g 1 Corrected for residual DMF.

l Measured by nuclear magnetic resonance s ectrosco a Contains 12.1% DME` of solvation. p py Percent by weight r Example HECl NaOH PI Remarks 1.8 4 2 Translucent gel.

1 4 2 Opaque gel; s1. shrinkage. 1 4 1 Opaque gel. 1 4 0.50 Translucent gel. 1 2 0. 25 D0 Transparent gel; 25% shrinkage.

1 HEC=Hydroxyetl1yl cellulose (Natrosal 250 Hercules Powder).

EXAMPLES VIII-XI When the following examples were conducted according to the techniques of the preceding examples, in each case no gel was formed. These examples serve to indicate the unexpectedness of the gelation property of the compositions of the present invention.

POaH COgUl-Ia C 05H S-CzHs S H Percent by weight l Example HEC1 NaOH PI Remarks 1.8 4 o No lann. 0.75 o 2 o. 5 1.o o 1 D0. 0.125 4 a Do.

1 HEC=Hydroxyethy1 cellulose (N atrosal 250 Hercules Powder). 0i

O20-NH3 O-l-CH; CHzOH NH?.

. OH Modifications of the invention l It should be understood that the invention is capable of a variety of modiiications and variations which will be made apparent to those skilled in the art by a reading of the speciication and which are to be included within 0 O What is claimed is: 1. A gel composition substantially insoluble in water H Ir GHB H If CH3 som [OBCH o?) CH prepared by reacting at a pH above 7, an alkali metal hydroxide or alkaline earth metal hydroxide with a compound containing metal isocyanurate groups, in the pres- 1 ence of hydroxyethyl cellulose wherein there are present compound, and from 0.15 to about 20% by weight of said hydroxyethyl cellulose said compound containing iso- Of (13N :ro NHNH 0:? CH' cyanurate groups having the general structure:

X I I I I l Il, l

N.. I Y m Y n s v wherein R is a divalent hydrocarbon radical or hydrocarbon radical substituted with groups selected from the NR"2, -CONR2, -SO3R", -SO2R, -SOR, 40 phenyl, naphthyl, alkyl (1-40 carbon atoms), CHI@I -PO3R" cyclohexyl cyclopropyl, -OCOR", CH,

the spirit of the claims appended hereto.

0.2 to about by Weight of said isocyanurate salt @t to @fr0 3@ N (-R-)lm++l (-Mnm o1r=om :901cm GHz-Hi dass consisting of Nog c1, F, Br, I, CN, Co2

blew CH CH, where R" is hydrogen, lower alkyl or monovalent 50 radical corresponding to the aryl radicals described *CH@ CH' below:

(IHI 03H1 CHa-CH-CHg-Ch t 55 @-o-@- e' l I I v CH 0020113 l 60 CH3 Hi, I CIH2CH2 H CH:-CH=CH3 Y .f jj eee @amai Q i@ @gama (where H1=F, c1, Br or I), 75

i CH3 X is selected from the group consisting of metals, hy-

drogen, and quaternary ammonium radicals,

t A is a monovalent organic radical selected from the group consisting of -NCO, -NHCOZRQ -NHCO R is a monovalent hydrocarbon radical or hydrocarbon radical substituted with groups selected from the class consisting of NO2, C1, F, Br, I, CN, CO2 R", -CO-R", -O-R, -SR", NR2, -CONR"2, -SO3R, -SO2R", -SOR, phenyl, naphthyl, alkyl (1-40) carbon atoms), P03 R, cyclohexyl where R" is hydrogen, lower valkyl or monovalent radical corresponding to the aryl radicals described above;

m is the average number of trisubstituted isocyanurate rings per molecule and is a positive number from zero to about 400,

n is the average number of isocyanurate acid and/r isocyanurate salt groups and is a positive number from about 1 to about 10,000, wherein, Zm-l-ng-l-l :the average number of divalent R groups and is a positive integer from 2 to about 11,000, and wherein m-l-2 is the avera-ge number of A groups and is a positive integer from 2 to about 2,000, and wherein there are no N-to-N bonds and no `A;-t ".\-N bonds, and no A--to-A bonds and no R-to-R bonds.

2. A composition according'to claim 1 wherein R is selected from the group of organic radicals show rrinv the following structure:

CzuHn .'POaH COgCH| v C 02H Il i o H-lI-CH. vH-N-c--cm som soton. oas-on @aa-aas- C H=CH1 P OaCH; GHz-Hl ,5 um@ @4m-@- i a @a CH3 CH, CH,

and wherein the substituted hydrocarbons are selected from hydrocarbon radicals substituted with groups selected from the class consisting of: NO2, Cl, F, Br, I, CN, -CO2R, -CO-- -O-- -SR", -NR2", -CONR2", -SO3R, SO2R", -SOR", phenyl, naphthyl, alkyl (1 40 carbon atoms), -PO3R, cyclohexyl, cyclopropyl, -OCOR,

where R is hydrogen, lower alkyl or monovalent radicals corresponding to the aryl radicals described in the structure above.

3. Composition according to claim 1 wherein X is selected from the group consisting of hydrogen, quaternary ammonium radicals and metal radicals selected from the following groups of the Periodic Table; Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIa.

4. Composition according to claim 1 wherein m is a positive integer from to about 200, wherein n is a positive integer from 3 to about 100, and wherein 2m|w+1 is a positive integer from 4 to about 140, and wherein m-l-Z is a positive integer from about 2 to about 200.

5. Composition according to claim 1 wherein R contains from 1 to 10 carbon atoms and is selected 4from the 6. Composition according to claim 1 wherein X is selected from the group consisting of: Li, Na, K, Rb, Cs, A-g, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Se, Y, La, and the other rare earths, Ac, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, and Ir.

A 'UNHED STATES PATENT mmm CEQTTE @1? QRRECN Patent No. 3,789,010 January 29, 1974 Dated Inventor(s) C. T. Preslel7 et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col 1, line 32: Delete "with Class" and insert --within C1ass.

co1. 2, line 56: Delete:

CHB- c? CH2 and insert:

Signed and sealed this 12th day zvfV November 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. 4 Co MARSHALL DANN Attestng Officer Commissioner of Patents F ORM PO-IOSO l 10-59) USCOMM-DC 603764369 n u s ooyznnucm Pnmrmo ofrlcz; un n-ns-Ju FORM PO-OSO (1D-59) UNrrn STATES ".'PA'INT` orifice CERTFCATE 0F CBRECTIN vJanuary 29, 1974 Patent No. Dated It ls certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as' shown below:

Col l, line 32: Delete "with Class" and insert within Class.

Col. 2, line 56: Delete:

CH3 C CH2-- CH3 and insert:

co1. 2, 1in@ 68: Delete "so3R"-"V and Col. 3, line 54: Delete "0. 3" and insert O.2. g n i O insert= 0 f Col. 6, line 20. Delete 0kg-CH Signed and sealed this 12th c'iay of November 1974.

(SEAL) Attest:

MCCOY M. GIBSON JR. l C. MARSHALL DANN Attestng Officer Commissioner of Patents USCOMM-DC 60375-1369 e u s coylnnurnr murmur. omcz; un o--ul-Jn 

